JP2006517521A - Bactericidal mixtures based on triazolopyrimidine derivatives and azoles - Google Patents

Abstract

活性成分として、A) 式Ｉで表されるトリアゾロピリミジン誘導体と、B)ブロムコナゾール、ジフェノコナゾール、ジニコナゾール、フェンブコナゾール、フルキンコナゾール、フルシラゾール、ヘキサコナゾール、プロクロラズ、テトラコナゾール、トリフルミゾール、フルトリアホール、ミクロブタニル、ペンコナゾール、シメコナゾール、イプコナゾール、トリチコナゾールおよび、プロチオコナゾールからなる群から選択されるアゾール誘導体又はその塩若しくはアダクツとを、相乗的に有効な量で含む殺菌性混合物、植物病原性の有害な真菌を化合物ＩおよびII〜XVIIIの混合物を用いて抑制する方法、これらの混合物を含む物質、ならびに化合物ＩおよびII〜XVIIIの化合物の、かかる混合物を調製するための使用を記載する。[Chemical 1]

As active ingredients, A) a triazolopyrimidine derivative represented by Formula I, and B) bromconazole, difenoconazole, diniconazole, fenbuconazole, fluquinconazole, flusilazole, hexaconazole, prochloraz, tetraconazole, triflumi A bactericidal mixture comprising a synergistically effective amount of an azole derivative selected from the group consisting of sol, flutriahol, microbutanyl, penconazole, cimeconazole, ipconazole, triticonazole and prothioconazole, or a salt or adduct thereof. Method for inhibiting phytopathogenic harmful fungi with mixtures of compounds I and II to XVIII, substances containing these mixtures and the use of compounds of compounds I and II to XVIII for preparing such mixtures Is described.

Description

As an active ingredient, the present invention
A) Formula I:

A triazolopyrimidine derivative represented by:
B)
(1) Formula II:

Bromuconazole represented by and
(2) Formula III:

Difenoconazole represented by and
(3) Formula IV:

Diniconazole represented by
(4) Formula V:

Fenbuconazole represented by
(5) Formula VI:

Fluquinconazole represented by
(6) Formula VII:

Flusilazole represented by
(7) Formula VIII:

Hexaconazole represented by
(8) Formula IX:

Prochloraz represented by and
(9) Formula X:

Tetraconazole and
(10) Formula XI:

Triflumizole represented by
(11) Formula XII:

Futuria hall represented by
(12) Formula XIII:

Microbutanyl represented by
(13) Formula XIV:

Penconazole represented by
(14) Formula XV:

Cimeconazole represented by
(15) Formula XVI:

Ipconazole represented by and
(16) Formula XVII:

Triticonazole represented by
(17) Formula XVIII:

Prothioconazole represented by:
It relates to a bactericidal mixture comprising a synergistically effective amount of an azole derivative selected from the group consisting of or a salt or adduct thereof.

  The present invention further relates to a method of controlling harmful fungi using a mixture of compound I and at least one of compounds II to XVIII, use of at least one of compound I and compounds II to XVIII for preparing such a mixture, and It relates to a composition comprising these mixtures.

  A compound of formula I, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1,5-a ] Pyrimidines, their preparation and their action against harmful fungi are known from the literature (WO-A 98/46607).

  Mixtures of triazolopyrimidine derivatives with other active compounds are known in general manner from EP-A 988 790 and US 6,268,371.

  The synergistic mixture of triazolopyrimidines described in EP-A 988 790 is effective against various diseases of cereals, fruits and vegetables, especially wheat and barley mildew or apple gray mold. It has been described as having fungal activity.

The azole derivatives II to XVIII, their preparation and their action against harmful fungi are known per se:
Bromconazole (II),
1- [4-Bromo-2- (2,4-dichlorophenyl) tetrahydrofuran-2-ylmethyl] -1H- [1,2,4] triazole: Proc. Br. Crop Prot. Conf.-Pests Dis., 5- 6, 439 (1990);
Difenoconazole (III),
1- {2- [2-Chloro-4- (4-chlorophenoxy) phenyl] -4-methyl- [1,3] dioxolan-2-ylmethyl} -1H- [1,2,4] triazole: GB- A 2 098 607;
Diniconazole (IV),
1- (2,4-dichlorophenyl) -4,4-dimethyl-2- [1,2,4] triazol-1-ylpent-1-en-3-ol: CAS RN [83657-24-3];
Fenbuconazole (V),
3- (4-chlorophenyl) -2-phenyl-2- [1,2,4] triazol-1-ylpropionitrile: EP-A 251 775;
Fluquinconazole (VI),
3- (2,4-Dichlorophenyl) -6-fluoro-2- [1,2,4] -triazol-1-yl-3H-quinazolin-4-one: Proc. Br. Crop Prot. Conf.-Pests Dis ., 5-3 (1992), 411;
Flusilazole (VII),
1-{[Bis (4-fluorophenyl) methylsilanyl] methyl} -1H- [1,2,4] triazole: Proc. Br. Crop Prot. Conf.-Pests Dis., 1 (1984), 413;
Hexaconazole (VIII),
2- (2,4-dichlorophenyl) -1- [1,2,4] triazol-1-ylhexan-2-ol: CAS RN [79983-71-4];
Prochloraz (IX),
N- {propyl- [2- (2,4,6-trichlorophenoxy) ethyl]} imidazole-1-carboxamide: US-A 3 991 071;
Tetraconazole (X),
1- [2- (2,4-Dichlorophenyl) -3- (1,1,2,2-tetrafluoroethoxy) propyl] -1H- [1,2,4] triazole: Proc. Br. Crop Prot. Conf .-Pests Dis., 1 (1988), 49;
Triflumizole (XI),
(4-Chloro-2-trifluoromethylphenyl)-(2-propoxy-1- [1,2,4] triazol-1-ylethylidene) amine: JP-A 79/119 462;
Futuria Hall (XII),
1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- [1,2,4] triazol-1-ylethanol: CAS RN [76674-21-0];
Microbutanyl (XIII),
2- (4-Chlorophenyl) -2- [1,2,4] triazol-1-ylmethylpentanenitrile: CAS RN [88671-89-0];
Penconazole (XIV),
1- [2- (2,4-dichlorophenyl) pentyl] -1H- [1,2,4] triazole: Pesticide Manual, 12th Ed. (2000), page 712;
Cimeconazole (XV),
1- (4-fluorophenyl) -2- [1,2,4] triazol-1-yl-1-trimethylsilanylethanol: The BCPC Conference Pests and Diseases 2000, pp. 557-562;
Ipconazole (XVI),
2- (4-Chlorobenzyl) -5-isopropyl-1- [1,2,4] triazol-1-ylmethylcyclopentanol: EP-A 267 778;
Triticonazole (XVII),
5- (4-chlorobenzylidene) -2,2-dimethyl-1- [1,2,4] triazol-1-ylmethylcyclopentanol: EP-A 378 953; and prothioconazole (XVIII),
2- [2- (1-Chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro [1,2,4] triazole-3-thione: WO 96/16048.

  Bactericidal mixtures containing one of the azoles II to XVIII as one active compound component are known from EP-A 531 837, EP-A 645 091 and WO 97/06678.

  According to agricultural practice, repeated and exclusive application of individual active compounds in the control of harmful fungi often results in rapid selection of fungal strains that are developing natural or compatible resistance to the active compound in question Shows that happens. Thus, effective suppression of these fungi by the active compound in question is no longer possible.

  In order to reduce the risk of selecting resistant fungal strains, recently various active compounds are usually used to control harmful fungi. By combining active compounds with different mechanisms of action, it is possible to ensure successful inhibition over a relatively long period of time.

  The object of the present invention is to provide further compositions, especially for certain indications, for controlling harmful fungi from the viewpoint of effective resistance management and effective control of harmful fungi.

  We have achieved this object with a mixture comprising a triazolopyrimidine derivative of the formula I as active compound and an active compound from the group consisting of azoles II to XVIII as a further fungicidal active ingredient. I found it.

  The present invention therefore provides the first defined mixture. Furthermore, one simultaneous, ie together or separate application of compound I and compounds II to VVIII or sequential application of compound I and compounds II to VVIII is possible with harmful fungi that are possible with the individual compounds alone. It has been found that control superior to control is possible.

  The mixtures according to the invention are synergistic and are therefore particularly suitable for controlling harmful fungi and especially powdery and downy mildew fungi of cereals, vegetables, fruits, ornamental plants and grapes It is.

  As azole derivatives, the mixtures according to the invention comprise at least one compound of the formulas II to XVIII.

  Even if the ratio of the triazolopyrimidine derivative of formula I is small, the synergistic effect is sufficiently effective. The triazolopyrimidine derivative and azole are preferably used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.

  Since the nitrogen atom is basic, compounds I and II-XVIII can form salts or adducts with inorganic or organic acids or metal ions.

  Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.

  Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acid, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, Oxalic acid, alkyl sulfonic acid (sulfonic acid having a linear or branched alkyl group of 1 to 20 carbon atoms), aryl sulfonic acid or -disulfonic acid (phenyl and naphthyl having 1 or 2 sulfonic acid groups) Aromatic phosphonic acids (phosphonic acids having a linear or branched alkyl group of 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (1 or 2 phosphonic acid groups) Aromatic groups such as phenyl and naphthyl), alkyl and aryl groups may have further substituents, for example p- toluenesulfonic acid, salicylic, p- aminosalicylic acid, 2-phenoxybenzoic acid, and the like 2-acetoxybenzoic acid.

  Suitable metal ions are in particular the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, and even the second group, in particular calcium and magnesium, and the third and fourth groups, In particular, ions of elements of aluminum, tin and lead. If appropriate, the metal can exist in various valences it can take.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with bromuconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with difenoconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with diniconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with fenbuconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with fluquinconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with flusilazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with hexaconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with prochloraz.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with tetraconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with triflumizole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with flutriahole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with microbutanyl.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with penconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with cimeconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with ipconazole.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with triticonazo.

  Preference is given to mixtures of the triazolopyrimidine derivative of the formula I with prothioconazole.

  When preparing the mixture, it is preferred to use the pure active compounds I and II to XVIII, in addition to active compounds against harmful fungi or other pests, such as insects, spiders or nematodes, or else weeding or Growth regulating active ingredients or fertilizers can be added.

  A mixture of compound I and at least one of compounds II to XVIII, or at the same time, at least one of compounds I and II to XVIII, used together or separately, has a broad spectrum of phytopathogenic fungi, particularly ascomycetes ( It exhibits excellent action against harmful fungi from the classes of Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of these compounds have systemic effects and can therefore be used as leaf and soil action fungicides.

  They are a variety of agricultural plants such as cotton, vegetable plants (eg cucumbers, beans, tomatoes, potatoes and cucumbers), barley, grasses, oats, bananas, coffee, corn, fruit plants, rice, rye, soybeans, grapes Especially important for controlling a large number of fungi in wheat, ornamental plants, sugarcane and numerous seeds.

  They are particularly suitable for controlling the following phytopathogenic fungi: cereal Blumeria graminis, powdery cucumber Erysiphe cichoracearum and Sphaerotheca fuliginea, apple Podosphaera leucotricha, grape Uncinula necator, cereal Puccinia species Rhizoctonia species of cotton, rice and grass, Ustilago species of cereals and sugarcane, Venturia inaequalis of apples, Bipolaris and Drechslera species of cereals, rice and grass, Septoria nodorum of wheat, strawberries, vegetables, ornamental plants and Botrytis cinera of grapes, Banana, peanut and cereal Mycosphaerella species, wheat and barley Pseudocercosporella herpotrichoides, rice Pyricularia oryzae, potato and tomato Phytophthora infestans, cucumber and hop Pseudoperonospora species, grape Plasmopara viticola and vegetable and fruit Alternium species and also fruit Alternium species Verticillium species

  The mixtures according to the invention are preferably useful for controlling powdery mildew fungi in cereals, grapes and vegetable crops and ornamental plants.

  Furthermore, the mixtures according to the invention are also preferably active against harmful fungi from the class of Oomycetes, in particular against potato and tomato Phytophthora infestans.

  The mixtures according to the invention are also preferably suitable for controlling rice pathogens.

  Depending on the specific cultivation conditions of the rice plant, the requirements that a rice fungicide must meet are quite different from the requirements that a fungicide used in cereal or fruit cultivation must adapt. There are significant differences in modern systems of rice cultivation: in addition to spray application commonly used in many countries, in these systems the fungicide is applied during sowing or in a short period after sowing. Applied directly to the soil. The fungicide is taken into the plant via the roots, enters the plant fluid and is transported to the plant part to be protected. Therefore, a strong systemic action is essential for rice fungicides. In contrast, in cereal or fruit cultivation, fungicides are usually applied on the leaves or fruits; therefore, in these crops, the systemic action of the active compounds is less important.

  Furthermore, rice pathogens are typically different from cereal or fruit pathogens. Pyricularia oryzae (rice blast fungus), Cochliobolus miyabeanus (rice sesame leaf blight fungus) and Corticium sasakii (rice blight fungus) (synonymous with Rhizoctonia solani AG 1-IA) are the most common pathogens in rice plants. These do not come across as worth mentioning in other crop plants. Rhizoctonia solani is the only agriculturally important pathogen from the subclass Agaricomycetidae. In contrast to most other fungi, this fungus attacks plants not through spores but through mycelium infection.

  For this reason, knowledge about the fungicidal activity of active compounds in the cultivation of cereals or fruits cannot be applied to rice crops.

  Compound I and at least one of compounds II-XVIII can be applied simultaneously, i.e. together or separately or sequentially, the order of which generally depends on the result of the suppression measures. Does not affect.

  Depending on the type of effect desired, the application rate of the mixture according to the invention is 5 to 2000 g / ha, preferably 50 to 1500 g / ha, in particular 50 to 750 g / ha, especially in the case of a planted area.

  The application rate of compound I is 1-1000 g / ha, preferably 10-900 g / ha, in particular 20-750 g / ha.

  Correspondingly, the application rates of compounds II to XVIII are 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

  In the seed treatment, the application rate of the mixture is generally from 1 to 1000 g / 100 seed kg, preferably from 1 to 200 g / 100 seed kg, in particular from 5 to 100 g / 100 seed kg.

  In controlling phytopathogenic harmful fungi, application of at least one separate or joint application of compound I and compounds II to XVIII, or application of a mixture of compounds I and II to XVIII, before or after planting, or It is carried out by spraying or dusting seeds, seedlings, plants or soils before or after plant emergence.

  The bactericidal synergistic mixture according to the invention or at least one of compound I and compounds II to XVIII is, for example, in the form of a directly sprayable solution, dust and suspension or highly concentrated aqueous, oily or other suspension. Can be prepared in the form of a suspension, dispersion, emulsion, oil dispersion, paste, dust, widespread composition or granule and applied by spraying, atomizing, dusting, widespread, or irrigation . The application form depends on the particular purpose, and in each case a fine and uniform distribution of the mixture according to the invention must be ensured.

  Compounds I and II-XVIII, mixtures or suitable formulations can be used to separate or separate plants, seeds, soils, areas, materials or spaces from which harmful fungi, their habitats or harmful fungi are to be absent. Is applied by treatment with a fungicidally effective amount of at least one of compounds I and compounds II to XVIII.

  Application may be carried out before or after infection by harmful fungi.

The formulations are prepared in a known manner, for example by diluting the active compound with solvents and / or carriers, if desired with emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially as follows:
-Water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg mineral oil fraction), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, γ-butyrolactone), pyrrolidone (NMP, NOP), acetate (glycol diacetate), glycol, fatty acid dimethylamide, fatty acid and fatty acid ester. In principle, solvent mixtures may be used;
-Carriers, such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates); emulsifiers, eg nonionic and anionic emulsifiers (eg polyoxy) Ethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin sulfite waste liquors and methylcellulose.

  Suitable surfactants include lignosulfonic acid, naphthalene sulfonic acid, phenol sulfonic acid, dibutyl naphthalene sulfonic acid, alkylaryl sulfonic acid, alkyl sulfuric acid, alkyl sulfonic acid, fatty alcohol sulfuric acid, fatty acid and sulfated fatty alcohol glycol ether alkali. Metal salts, alkaline earth metals and ammonium salts, as well as condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol Octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, Rilphenyl polyglycol ether, alkylaryl polyether alcohol, alcohol and fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sal Fight waste liquid as well as methylcellulose.

  Substances suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are medium to high boiling mineral oil fractions such as kerosene or diesel oil, as well as coal tar oil and oils of vegetable or animal origin, Aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexane, isophorone, highly polar solvents such as dimethyl Sulfoxide, N-methylpyrrolidone or water.

  Dusts, widespread materials and dusts can be prepared by mixing the active material with a solid carrier or by grinding together.

  Granules, such as coated granules, impregnated granules and uniform granules, can be prepared by combining the active compound with a solid carrier. Examples of solid supports are mineral soils such as silica gel, silicates, talc, kaolin, activated clay (attaclay), limestone, lime, chalk, boll clay, loess, clay, dolomite, diatomaceous earth , Calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic minerals, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin such as cereal meal, bark meal, wood meal and Nut shell meal, cellulose powder and other solid carriers.

  In general, the formulations contain 0.01 to 95% by weight of active compound, preferably 0.1 to 90%. The active compounds are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations:
1. Products for dilution with water
A) Water-soluble concentrate (SL)
10 parts by weight of active compound are diluted in water or a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active compound dissolves upon dilution with water.

B) Dispersible concentrate (DC)
20 parts by weight of the active compound are dissolved in cyclohexane with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable concentrate (EC)
15 parts by weight of the active compound are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and ethoxylated castor oil (both 5%). Dilution with water gives an emulsion.

D) Emulsified liquid (EW, EO)
40 parts by weight of the active compound are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and ethoxylated castor oil (5% each). This mixture is introduced into water using an emulsifier (Ultraturax) to make a uniform emulsion. Dilution with water gives an emulsion.

E) Suspension (SC, OD)
In a ball mill equipped with a stirrer, a dispersant, a wetting agent, and water or an organic solvent are added to 20 parts by weight of the active compound and finely pulverized to obtain a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.

F) Water dispersible granules and water soluble granules (WG, SG)
A dispersant and a wetting agent are added to 50 parts by weight of the active compound, and the mixture is finely pulverized, and water-dispersible or water-soluble granules are produced using an apparatus (for example, extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.

G) Water-dispersible powder and water-soluble powder (WP, SP)
75 parts by weight of active compound are ground in a rotor / stator mill with the addition of dispersant, wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.

2. Products applied without dilution
H) Dustable powder (DP)
5 parts by weight of active compound are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dustable product.

I) Granules (GR, FG, GG, MG)
0.5 parts by weight of active compound are finely ground and combined with 95.5% carrier. Current methods are extrusion, spray drying or fluidized bed. This gives granules to be applied undiluted.

J) ULV solution (UL)
10 parts by weight of the active compound are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted.

  The active compounds are used as such, in the form of their preparations or in the use forms prepared therefrom, for example directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, It can be used in the form of a widespread composition or in the form of granules, using spraying, atomizing, dusting, widespreading, or irrigation. The use forms all depend on their intended purpose; in each case it is intended to ensure the finest possible distribution of the active compounds of the invention.

  Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare an emulsion, paste or wettable powder, the material can be homogenized in water as is or dissolved in an oil or solvent and using a wetting agent, thickening agent, dispersing agent or emulsifier. Alternatively, concentrates suitable for dilution with water, composed of active substance, wetting agent, thickening agent, dispersing or emulsifying agent and, if appropriate, solvent or oil may be prepared.

  The active compounds in ready-to-use preparations can vary over a relatively wide range. Generally, it is 0.0001 to 10%, preferably 0.01 to 1%.

  The active compounds can also be used successfully in ultra low volume (ULV) processes, applying compositions containing more than 95% by weight of active compounds or applying active compounds without additives I can even do it.

  Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides or bactericides can be added to the active compound, if appropriate, just prior to use (tank mixing). These drugs can be added to the drug of the present invention at a weight ratio of 1:10 to 10: 1 and mixed.

Use Examples The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiments.

  The active compounds were prepared separately or together as a 0.25 wt% stock solution of the active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution. The active compound or mixture was diluted with water to the indicated concentration.

Evaluation is carried out by measuring the infected leaf area as a percentage. Convert these percentages to potency. The efficacy (W) is Abbot's formula as follows:
W = (1-α / β) · 100
[Wherein α corresponds to% fungal infection of treated plants and β corresponds to% fungal infection of untreated (control) plants].

  A potency of 0 means that the level of infection of the treated plant corresponds to the level of infection of the untreated control plant; a potency of 100 means that the treated plant was not infected.

The expected efficacy of a mixture of active compounds is Colby's formula (RS Colby, Weeds 15, 20-22 (1967)):
E = x + y−x · y / 100
[Where:
E is the expected potency expressed as% of untreated control when a mixture of active compounds A and B is used at concentrations a and b,
x is the potency expressed as% of untreated control when active compound A is used at concentration a,
y is the potency expressed as% of untreated control when active compound B is used at concentration b. ]
And compare with the observed potency.

Use Example 1 The rice seedling leaves of Tai-Nong 67, a protective active cultivar against rice blast caused by Pyricularia oryzae, are grown in pots, and until the droplets drop on them An aqueous suspension having a concentration of the active compound was sprayed. The next day, the plants were inoculated with an aqueous suspension of Pyricularia oryzae spores. The test plants were then placed in a climate control room at 22-24 ° C. and 95-99% relative atmospheric humidity for 6 days. Thereafter, the degree of infection on the leaves was visually confirmed.

Example 2 Activity against brown spots of rice caused by Cochliobolus miyabeanus, growing rice seedlings of the protected cultivar “Tai-Nong 67” in pots, An aqueous suspension having the active compound concentrations described below was sprayed. The next day, the plants were inoculated with an aqueous suspension of Cochliobolus miyabeanus spores. The test plants were then placed in a climate control room at 22-24 ° C. and 95-99% relative atmospheric humidity for 6 days. Thereafter, the degree of infection on the leaves was visually confirmed.

Use Example 3 An aqueous suspension having the concentration of the active compound described below was sprayed until droplets dropped on the leaves of the active potted grapes against the perotospora of grapes caused by Plasmopara viticola . The next day, the lower suspension of the leaves was inoculated with an aqueous suspension of Plasmopara viticola fungus spores. The grapes were then first placed in a steam saturated room at 24 ° C. for 48 hours and then in a greenhouse at 20-30 ° C. for 5 days. After this period, the plants were again placed in a humid room for 16 hours to promote sporangiophore rupture. Subsequently, the extent to which infection occurred on the lower side of the leaves was visually confirmed.

  The test results show that for all mixing ratios, the observed potency of the mixtures according to the invention is considerably higher than expected using the Colby equation.

Claims (10)

As an active ingredient
A) Formula I:

A triazolopyrimidine derivative represented by:
B)
(1) Formula II:

Bromuconazole represented by and
(2) Formula III:

Difenoconazole represented by and
(3) Formula IV:

Diniconazole represented by
(4) Formula V:

Fenbuconazole represented by
(5) Formula VI:

Fluquinconazole represented by
(6) Formula VII:

Flusilazole represented by
(7) Formula VIII:

Hexaconazole represented by
(8) Formula IX:

Prochloraz represented by and
(9) Formula X:

Tetraconazole and
(10) Formula XI:

Triflumizole represented by
(11) Formula XII:

Futuria hall represented by
(12) Formula XIII:

Microbutanyl represented by
(13) Formula XIV:

Penconazole represented by
(14) Formula XV:

Cimeconazole represented by
(15) Formula XVI:

Ipconazole represented by and
(16) Formula XVII:

Triticonazole represented by
(17) Formula XVIII:

Prothioconazole represented by:
A bactericidal mixture comprising a synergistically effective amount of an azole derivative selected from the group consisting of: or a salt or adduct thereof. 2. The bactericidal mixture according to claim 1, wherein the weight ratio of the triazolopyrimidine of formula I to the respective triazole of formulas II to XVIII is from 100: 1 to 1: 100. A bactericidal composition comprising the bactericidal mixture according to claim 1 or 2 and a solid or liquid carrier. A method for controlling phytopathogenic harmful fungi, wherein the harmful fungi, their habitat or plants, seeds, soil, regions, materials or spaces to be kept free of them are claimed in claim 1. 4. A process comprising treating with a triazolopyrimidine of formula I and an azole of formula II to XVIII according to claim 1 or with a composition according to claim 3. 5. A compound according to claim 4 wherein the compound of formula I according to claim 1 and at least one compound of formulas II to XVIII according to claim 1 are applied simultaneously, i.e. together or separately or sequentially. Method. 6. The method according to claim 4 or 5, wherein the bactericidal mixture according to claim 1 or the compound of formula I and at least one compound of formulas II to XVIII are applied in an amount of 5 to 2000 g / ha. 7. A method according to any one of claims 4 to 6, wherein harmful fungi from the class of Oomycetes are suppressed. The method according to any one of claims 4 to 6, wherein harmful fungi that are rice pathogens are suppressed. A seed comprising the mixture according to claim 1 or 2 in an amount of 1 to 1000 g / 100 kg. Use of compounds I and II to XVIII according to claim 1 for the preparation of a bactericidal composition according to claim 3.